Organometallic solution based high resolution patterning compositions and corresponding methods
Organometallic radiation resist compositions are described based on tin ions with alkyl ligands. Some of the compositions have branched alkyl ligands to provide for improved patterning contrast while maintaining a high degree of solution stability. Blends of compounds with distinct alkyl ligands can provide further improvement in the patterning. High resolution patterning with a half-pitch of no more than 25 nm can be achieved with a line width roughness of no more than about 4.5 nm. Synthesis techniques have been developed that allow for the formation of alkyl tin oxide hydroxide compositions with very low metal contamination.
1. A method for forming a radiation sensitive, patternable organotin oxide-containing film, the method comprising:
depositing a tin precursor composition to form a coating on a substrate surface, the tin precursor composition having a radiation sensitive Sn—C bond and a hydrolysable ligand; and
baking the substrate with the coating,
wherein the hydrolysable ligands are replaced by hydroxo ligands during depositing and baking to form the radiation sensitive, patternable organotin oxide-containing film, the film comprising a composition described by the formula (R) z SnO 2-z/2-x/2 (OH) x , (0<(x+z)<4), where R is an alkyl, cycloalkyl or substituted alkyl moiety having from 1 to 31 carbon atoms.
2. The method of claim 1 wherein the film comprises Sn—OH and Sn—O—Sn bonds and the radiation sensitive Sn—C bond.
3. The method of claim 1 wherein the Sn—C bond can be cleaved by at least one of EUV, UV, and e-beam radiation.
4. The method of claim 1 wherein the hydrolysable ligand comprises an alkoxide, an alkylamide, an alkynide, an azide, a dialkylamide, or a mixture thereof.
5. The method of claim 1 wherein the tin precursor composition comprises t-butyl tris(dimethylamido)tin, i-propyl tris(dimethylamido)tin, t-butyl tris(diethylamido)tin, i-propyl tin trichloride, or combinations thereof.
6. The method of claim 1 wherein the depositing is by a vapor-based deposition process comprising chemical vapor deposition (CVD) or physical vapor deposition (PVD).
7. The method of claim 1 wherein the depositing is by a spin-coating, spray coating, dip coating, knife edge coating, or printing process or combinations thereof.
8. A method for patterning comprising:
forming a radiation sensitive, patternable organotin oxide-containing film using the method of claim 1 ; and
exposing the film to at least one of EUV, UV, and e-beam radiation in a pattern to form exposed portions and unexposed portions that results in cleaving of the Sn—C bond in the exposed portions.
9. The method of claim 8 wherein the film is at least partially condensed in the exposed portions.
10. The method of claim 8 wherein the unexposed portions are soluble in organic solvents.
11. The method of claim 8 wherein the exposure renders the exposed portions insoluble in organic solvents.
12. The method of claim 8 further comprising removing at least a portion of the exposed portion in a development step.
13. The method of claim 12 wherein the exposed portion is removed by an aqueous base in the development step.
14. The method of claim 1 wherein the substrate comprises a semiconductor wafer.
15. The method of claim 1 further comprising contacting the tin precursor composition with ambient water vapor.
16. The method of claim 15 wherein the contacting is performed during the depositing.
17. An article comprising a substrate with a surface, a first material at selected first regions along the surface and absent at first other regions along the surface, and a second material at selected second regions along the surface distinct from regions where the first material is present and absent at second other regions along the surface, the first material having a relative concentration of Sn—C bonds higher than the second material, wherein the first and the second materials have differential etch properties, and wherein the article can be alternatively subjected to positive tone patterning to selectively remove the second material or negative tone patterning to selectively remove the first material.
18. The article of claim 17 wherein the first material is soluble in at least some organic solvents and wherein the second material is not soluble in the organic solvents.
19. The article of claim 17 wherein the second material is soluble in aqueous bases and/or aqueous acids.
20. The article of claim 17 wherein the substrate comprises a semiconductor wafer and wherein baking is performed at about 45° C. to about 250° C. for about 0.1 minute to about 30 minutes.
21. The article of claim 17 wherein the article can be developed with a dry etch.
22. The article of claim 21 wherein the dry etch comprises halogen-based plasmas.
23. The article of claim 17 wherein the first and the second materials comprise one or more functional non-tin metals.
24. The article of claim 17 wherein baking is performed at about 45° C. to about 250° C. for about 0.1 minute to about 30 minutes.
25. A method for forming a radiation sensitive, patternable organotin oxide-containing film, the method comprising:
depositing a tin precursor composition to form a coating on a substrate surface, the tin precursor composition having a radiation sensitive Sn—C bond and a hydrolysable ligand, wherein the hydrolysable ligand comprises an alkoxide, an alkylamide, an alkynide, an azide, a dialkylamide, or a mixture thereof,
wherein the hydrolysable ligands are replaced by hydroxo ligands through hydrolysis during depositing to form the radiation sensitive, patternable organotin oxide-containing film, the film comprising a composition described by the formula (R) z SnO 2-z/2-x/2 (OH) x , (0<(x+z)<4), where R is an alkyl, cycloalkyl or substituted alkyl moiety having from 1 to 31 carbon atoms.